Fluorescence and phosphorescence of tryptophan in peptides of different length and sequence.

To interpret accurately protein fluorescence and phosphorescence, it is essential to achieve a better understanding of the luminescence properties of tryptophan (Trp, or W) in peptides. In published literature data on luminescence of peptides of varied length are scarce. This article describes studies of fluorescence and phosphorescence properties of the eight Trp-containing synthetic peptides: WAK, AWK, SWA, KYLWE, AVSWK, WVSWAK, WAKLAWE, and AVSWAKLARE. The aim was to investigate which factors influence the fluorescence yield and phosphorescence-spectra and lifetimes. Absorption spectra, room temperature fluorescence emission and corresponding excitation spectra and time-resolved phosphorescence spectra (77K) have been recorded; the dependence of the fluorescence quantum yield on the specific peptide and its variation with the wavelength of excitation has been studied. The changes in fluorescence yield and shape of phosphorescence spectra are explained in terms of internal electron and proton transfer. The structured phosphorescence spectrum originates from proton transfer occurring upon excitation of Trp, while electron transfer gives rise to a non-structured luminescence spectrum. There is also electron transfer from higher vibronic S1 states. In the peptides there is higher probability of electron transfer than in Trp alone. The obtained data are interpreted in light of the peptides' sequence, length and conformation.

Excited state structural changes of 10-cyano-9-tert-butyl-anthracene (CTBA) in polymer matrices.

Two main deactivation processes are suggested to be present in the electronic excited state of 10-cayano-9-tert-butyl-anthracene (CTBA): one leading to the Dewar strucure resulted from photochemical effect, similar to the case of 9-tert-butyl-anthracene (TBA), which is enhanced in solution, and another leads to a more planar structure leading to a Charge Transfer (CT) state and is enhanced in polymers. The presence of donor (tert-butyl group) and an acceptor (cyano group) along the line of 9,10 positions in CTBA confirm our hypothesis of CT state. Our suggestions were supported by steady state and time resolved fluorescence spectra results.

Single shot laser flash photolysis with a fibre-coupled reference beam monitor.

In the standard nanosecond laser photolysis method for kinetic studies, a Q-switched laser generates transient species, and absorption spectrophotometry provides a measure of their concentrations. The sample is placed between the monitoring source (a pulsed xenon arc or a flash lamp) and a monochromator, and a photomultiplier tube (PMT) is used for measuring the intensity of the light leaving the exit slit of the monochromator. With this (single-beam) arrangement, the laser-induced change in the absorbance of the sample, ΔA, can be calculated only if the intensity of the monitoring beam remains constant during the time interval of interest. When this condition is not fulfilled, a second measurement of the PMT output is made after blocking the path of the laser beam, but shot-to-shot variations in the output of the monitoring source vitiate the analysis when ΔA is small. To overcome this problem, double-beam versions were developed in the last century, but the single-beam version still enjoys greater popularity. With a view to making the double-beam method easily implementable, some simple modifications are introduced, which permit the conversion of an existing laser kinetic spectrometer into a double-beam variant (with one or two monochromators).

Atmospheric deposition of major and trace elements in Amman, Jordan.

Wet and dry deposition samples were collected in the capital of Jordan, Amman. Concentrations of Al, Ba, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, V, Zn, Fe, Sr, Mg2+, Ca2+, Na+, K+, Cl-, NO3- and SO(4)(2-), along with pH were determined in collected samples. Mean trace metal concentrations were similar or less than those reported for other urban regions worldwide, while concentrations of Ca2+ and SO(4)(2-) were among the highest. High Ca2+ concentrations were attributed to the calcareous nature of the local soil and to the influence of the Saharan dust. However, high SO(4)(2-) concentrations were attributed to the influence of both anthropogenic and natural sources. Except for Cl-, NO3-, SO(4)(2-) and Cu, monthly dry deposition fluxes of all measured species were higher than wet deposition fluxes. The annual wet deposition fluxes of trace metals were much lower than those reported for other urban areas worldwide.

Formation and geminate quenching of singlet oxygen in purple bacterial reaction center.

The phosphorescence of singlet oxygen ((1)X( *)) photosensitized by the carotenoidless reaction center (RC) of Rhodobacter sphaeroides R26.1 has been investigated, using H(2)O and D(2)O as the suspending media. To enhance (under neutral conditions) the triplet quantum yield of the special pair P(870) (P) by the radical pair mechanism, the quinone acceptor Q(A) was removed by means of a chemical treatment. The phosphorescence signal fits the functional form P(0)[exp (-t/tau)-exp(-t/zeta)], regardless of whether (1)X( *) is sensitized by P(dagger) or M(dagger) (where the dagger denotes triplet excitation and M is a water-soluble molecule). The time constant zeta was identified with the decay time of (1)X( *); when P(dagger) is the sensitizer, one finds zeta(P)((1))=3.3+/-0.3 micros, and zeta(P)((2))=34+/-3 micros, where the superscripts 1 and 2 refer to H(2)O and D(2)O, respectively; the corresponding values for sensitization by M(dagger) (in the absence of RC) are zeta(M)((1))=3.7+/-0.4 micros, and zeta(M)((2))=75+/-5 micros. The addition of RC's to the solution of M in D(2)O reveals that the RC is a quencher of (1)X( *); however, for equal concentrations of the RC, zeta(P)((2))

Structural characterization of new Cd(2+) fluorescent sensor based on lumazine ligand: AM1 and ab initio studies.

6-Thienyllumazine (TLM) is synthesized as a new fluorescent sensor that is capable of indicating selectively the presence of Cd(2+) ion via a fluorescence signal. Experiment has been performed in the presence of Ni(2+), Co(2+), Cu(2+), Ag(+), Mn(2+), Hg(2+), Zn(2+), Pb(2+), and Mg(2+) metal ions in aqueous solutions. The product was characterized by elemental analysis, mass, and NMR spectra. The spectral characteristics (maxima, quantum yields, Stokes shift, and lifetimes) of TLM in organic and aqueous solvents have been studied with the help of absorption and fluorescence spectroscopy, as well as, using time dependent spectrofluorimetry (single photon counting technique). The fluorescence dependence of TLM on the pH has also been investigated. The experimental results indicate that TLM exists in two ionic forms: neutral (acid) and anion (base). Electronic structure calculations of TLM were carried out using Semiempirical Austin Model 1 (AM1) and ab initio Hartree-Fock (HF) with 6-31G* basis set and using Gaussian 03 program. Absorption energies for TLM have been calculated using ZINDO method. The theoretical results confirm the presence of the thiophene and pteridine rings in two conformations: twisted at angle of about 35 degrees in the excited state and coplanar in the ground state.

Singlet oxygen quenching by thione analogues of canthaxanthin, echinenone and rhodoxanthin.

Thione analogues of three naturally occurring carotenones (canthaxanthin, echinenone, and rhodoxanthin) were synthesized just over ten years ago, and it was reported that substitution of the oxygen atom by sulphur brings about a large red shift and some broadening in the optical absorption spectrum of the compound. Since the three carotenothiones are scarce, determination of their molar absorption coefficients presents a challenge. A method for relating the molar absorption coefficient of a carotenothione (Car-S) to that of its ketone analogue (Car-O) has been developed, which has revealed that the peak molar absorption coefficient of a Car-S is only about 60% of the corresponding value for Car-O. Using methylene blue as the sensitizer and acetonitrile as the solvent, we have also investigated the quenching (under photostationary conditions) of the 1270nm phosphorescence emission of singlet oxygen by each of the six carotenoids. The data conform to the Stern-Volmer relation, and show that substitution of a carbonyl oxygen atom by sulphur does not lead to an appreciable change in the value of the quenching constant, which is close to 1.5 x 10(10)M(-1)s(-1) for all six quenchers.

Ab Initio calculations of the stabilization energies of the conformational and the structural isomers of C(3)H(7)X where X = F, Cl, and Br.

HF, MP2, and B3LYP calculations with different basis sets have been used in the computation of the stabilization energies of C(3)H(7)X isomers, where X is F, Cl, and Br. The experimental stabilization energies of the structural isomers of C(3)H(7)Cl and C(3)H(7)Br have been reproduced via B3LYP calculations. However, the calculated stabilization energies of fluoropropane isomers from their reported enthalpies of formation have been reproduced in all methods of calculations in present work. The experimental relative stabilities of the gauche conformers of 1-fluoro-, 1-chloro-, and 1-bromopropanes have been also reproduced via some of the used calculations in the present work. The effect of the geminal interactions on X atomic charges and on the C-X and C-C bond lengths in halopropane isomers are also discussed.